CN104650324B - The modified polymer and its manufacturing method containing fluoro oxyalkylene group of allyl - Google Patents
The modified polymer and its manufacturing method containing fluoro oxyalkylene group of allyl Download PDFInfo
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- CN104650324B CN104650324B CN201410677964.XA CN201410677964A CN104650324B CN 104650324 B CN104650324 B CN 104650324B CN 201410677964 A CN201410677964 A CN 201410677964A CN 104650324 B CN104650324 B CN 104650324B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
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Abstract
The present invention provides a kind of polymer containing fluoro oxyalkylene group, and other than water-repellent oil-repellent, release property, chemical resistance, lubricity, durability, soil resistance and fingerprint easily wiping property, thermal stability, chemical stability are excellent.A kind of modified polymer containing fluoro oxyalkylene group of allyl, it is represented by the following general formula (1), and with the number average molecular weight of polystyrene conversion for 1,000~50,000.Also, in formula, Rf be the polymer residue m containing fluoro oxyalkylene group of 1 valence perhaps divalent be 1 perhaps 2 X be F or CF3, the integer that n is 0~10, α is 1 or 2.
Description
Technical field
The present invention relates to a kind of novel polymer containing fluoro oxyalkylene group (fluorooxyalkylene group)
And its manufacturing method.
Background technique
Polymer containing fluoroalkylene is used for paper, fibre by the way that end is Organo-modified using various reactivity
Water-repellent oil-repellent antifouling agent, the lubricant of magnetic recording media, the oil-proofing agent of precision instrument, release agent, cosmetics and the protection of dimension etc.
Film etc..
Especially by the end of the polymer containing fluoroalkylene, via ehter bond (- C-O-C- key) by hydrolyzable
Property it is silyl-modified at perfluoropolyether-modified silane used as protective film etc., a kind of performance water-repellent oil-repellent can be provided
The surface (patent document 1) of property, release property, chemical resistance, lubricity, durability, soil resistance and fingerprint easily wiping property etc..But
As-C-O-C- the key contained in the perfluoropolyether-modified silane between carbon and carbon have oxygen atom (hetero atom), because
This thermal stability, poor chemical stability, therefore be not suitable for requiring the purposes of these characteristics.
Furthermore, it is also proposed that it is a kind of via silicon oxygen bond by the polymer containing fluoroalkylene and hydrolyzable silicyl key
The method (patent document 2) of knot, but since manufacturing process complicates, or needed when for vapor deposition treatment due to molecular weight becomes larger
More energy etc. is wanted, therefore, hardly possible is referred to as to be conducive to industrial method.
On the other hand, it provides in the compound as shown in following reaction equations containing more low molecular fluoroalkylene
One example (non-patent literature 1) of the allylation of terminally iodized object.
The allylation of the terminally iodized object of fluoroalkylene:
The allylation of fluoroalkylene end diiodomethane (methylene iodide):
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2003-238577 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2011-116947 bulletin
Non-patent literature
Non-patent literature 1:J.Org.Chem.1998,63,6302-6308
Summary of the invention
The present invention is in view of the above situation to complete, and its purpose is to provide a kind of polymerizations containing fluoro oxyalkylene group
Object, other than water-repellent oil-repellent, release property, chemical resistance, lubricity, durability, soil resistance and fingerprint easily wiping property, heat
Stability, chemical stability are excellent.
To solve the above-mentioned problems, the present invention provides a kind of polymer containing fluoro oxyalkylene group that allyl is modified,
Represented by it is by the following general formula (1), and with the number average molecular weight of polystyrene conversion for 1,000~50,000.
(in formula, Rf be the polymer residue m containing fluoro oxyalkylene group of 1 valence perhaps divalent be 1 perhaps 2 X be F or
CF3, the integer that n is 0~10, α is 1 or 2.)
If it is the modified polymer containing fluoro oxyalkylene group of such allyl, due to being free of in polymer ends
There is hetero atom, and bond sites are only formed by carbon-to-carbon (C-C) key, thus, it is possible to obtain in addition to water-repellent oil-repellent, release property, resistance to
Chemically, other than lubricity, durability, soil resistance and fingerprint easily wiping property, the excellent polymerization of thermal stability, chemical stability
Object.
Wherein, preferably, the α in aforementioned formula (1) is 1, and the aforementioned polymer residue containing fluoro oxyalkylene group is
By the residue of 1 valence represented by the following general formula (2).
(in formula, p, q, r, s are respectively 0~200 integer, and p+q+r+s=4~200, each repetitive unit can be any
Ground bond, Y are F or CF3。)
Also, preferably, the α in aforementioned formula (1) is 2, and the aforementioned polymer residue containing fluoro oxyalkylene group is
By the residue of the divalent represented by the following general formula (3).
(in formula, p ', q ', r ', s ' are respectively 0~200 integer, and p '+q '+r '+s '=4~200, each repetitive unit
It can arbitrarily be bonded, Y ' is F or CF3。)
If it is such polymer containing fluoro oxyalkylene group, can be made by the effect of above-mentioned fluoro oxyalkylene group
The surface free energy amount of polymer becomes smaller, obtain water-repellent oil-repellent, release property, chemical resistance, lubricity, durability, soil resistance,
And the fingerprint easily more excellent polymer of wiping property.
Further, the present invention provides a kind of manufacturing method of polymer containing fluoro oxyalkylene group that allyl is modified,
It is the method for manufacturing the modified polymer containing fluoro oxyalkylene group of foregoing allylic, is made by the following general formula (4) institute table
The terminally iodized object polymer containing fluoro oxyalkylene group and allyl trialkyltin (allyltrialkyltin) shown is certainly
By reacting in the presence of base initiator.
(in formula, Rf be the polymer residue m containing fluoro oxyalkylene group of 1 valence perhaps divalent be 1 perhaps 2 X be F or
CF3, the integer that n is 0~10, α is 1 or 2.)
If it is the manufacturing method of the modified polymer containing fluoro oxyalkylene group of such allyl, can make to manufacture
Process is easy, and can be conducive to industrial manufacture.
If it is the modified polymer containing fluoro oxyalkylene group of allyl of the invention, can be aoxidized by fluoro
The effect of alkenyl makes the surface free energy amount of polymer become smaller, and obtains water-repellent oil-repellent, release property, chemical resistance, lubricity, resistance to
Long property, soil resistance and the fingerprint easily more excellent polymer of wiping property, also, due to not containing hetero atom in polymer ends, and even
Knot position is only formed by carbon-to-carbon (C-C) key, thus, it is possible to obtain other than above-mentioned characteristic, further, thermal stability, chemistry
The excellent polymer of stability.Further, the polymerization containing fluoro oxyalkylene group modified if it is allyl of the invention
The manufacturing method of object does not need complicated manufacturing process then, can easily manufacture, and can be conducive to industrial manufacture.
Specific embodiment
Have the polymer containing fluoroalkylene of allyl in the linking part with allyl in end due to known
Position has hetero atom, therefore, thermal stability, poor chemical stability.The inventors of the present invention's discovery, if it is fluoro oxyalkylene will be contained
The method of the polymer (perfluoropolyether) of base directly allylation, then obtain a kind of polymer containing fluoro oxyalkylene group,
Bond sites do not have hetero atom, allyl are configured at end, i.e., the concatenating group of the distal portion of polymer is only by carbon-carbon bond
It is formed, and it was found that such polymer thermostable and chemical stability are excellent, thereby completing the present invention.
That is, the present invention is a kind of modified polymer containing fluoro oxyalkylene group of allyl, by the following general formula (1) institute
It indicates, and with the number average molecular weight of polystyrene conversion for 1,000~50,000.
(in formula, Rf be the polymer residue m containing fluoro oxyalkylene group of 1 valence perhaps divalent be 1 perhaps 2 X be F or
CF3, n be 0~10 integer, preferably 0 perhaps 1 α be 1 or 2.)
The polymer containing fluoro oxyalkylene group when the α in above-mentioned general formula (1) is 1, as 1 valence represented by by Rf
Residue, preferably the fluoro oxyalkylene group by 1 valence represented by the following general formula (2).
(in formula, p, q, r, s are respectively 0~200 integer, preferably 10~100 integer, and p+q+r+s=4~
200, preferably 10~100, each repetitive unit can be arbitrarily bonded, and Y is F or CF3。)
As the polymer residue containing fluoro oxyalkylene group of such 1 valence, specifically, may be exemplified as follows.
When the α in above-mentioned general formula (1) is 2, as the polymer containing fluoro oxyalkylene group by the divalent represented by Rf
Residue, preferably the fluoro oxyalkylene group by the divalent represented by the following general formula (3).
(in formula, p ', q ', r ', s ' they are respectively 0~200, preferably 10~100 integer, and p '+q '+r '+s '=4~
200, preferably 10~100, each repetitive unit can be arbitrarily bonded, and Y ' is F or CF3。)
As the polymer residue containing fluoro oxyalkylene group of such divalent, specifically, may be exemplified as follows.
By the quantity average mark of the modified polymer containing fluoro oxyalkylene group of the allyl represented by above-mentioned general formula (1)
Son amount is 1,000~50,000, preferably 1,500~10,000 range.If number average molecular weight is less than 1,000, then
It may be unable to give full play feature i.e. water-repellent oil-repellent, the soil resistance etc. of perfluoro alkylene ether structure, if it exceeds 50,
000, then the concentration of terminal functional group becomes too small, may decline with the reactivity or adhesion of substrate.In addition, in the present invention
Mentioned number average molecular weight refers to, measures under the following conditions, to utilize gel permeation chromatography (Gel
Permeation Chromatography, GPC) number average molecular weight of the polystyrene that is measured as standard substance.
[determination condition]
Eluent (eluent): hydrochlorofluorocarbons (hydrochlorofluorocarbon, HCFC) -225
Flow: 1mL/ minutes (min.)
Detector: evaporative light scattering detector
Tubing string: Tosoh company (TOSOH CORPORATION) TSKgel Multipore HXL-M (model) processed
7.8mm φ × 30cm uses 2
Tubing string temperature: 35 DEG C
Sample injection rate: 100 μ L (the HCFC-225 solution of 0.3 weight % of concentration)
If it is the modified polymer containing fluoro oxyalkylene group of such allyl, fluoro oxyalkylene group can be passed through
Effect so that the surface free energy amount of polymer is become smaller, obtain water-repellent oil-repellent, release property, chemical resistance, lubricity, durable
Property, soil resistance and the fingerprint easily excellent polymer of wiping property, also, due to not containing hetero atom, and linking part in polymer ends
Position is only formed with carbon-to-carbon (C-C) key, therefore other than above-mentioned characteristic, may further obtain thermal stability, chemical stabilization
The excellent polymer of property.
As the manufacturer by the modified polymer containing fluoro oxyalkylene group of the allyl represented by above-mentioned general formula (1)
Method, the manufacturing method of the modified polymer containing fluoro oxyalkylene group of preferably a kind of allyl are the aforementioned allyls of manufacture
The method of the modified polymer containing fluoro oxyalkylene group of base, being aoxidized containing fluoro represented by making by the following general formula (4)
Terminally iodized object polymer and the allyl trialkyltin of alkenyl react in the presence of a free-radical initiator.
(in formula, Rf be the polymer residue m containing fluoro oxyalkylene group of 1 valence perhaps divalent be 1 perhaps 2 X be F or
CF3, the integer that n is 0~10, α is 1 or 2.)
It can be used as allyl trialkyltin: for example, allyl tributyltin, allyl triphenyltin, allyl
Tin trimethyl, allyl tin triethyl, allyl tripropyl tin and allyl tribenzyltin etc..
As radical initiator, can be used: for example, azodiisobutyronitrile (azodiisobutyronitrile,
AIBN), 1,1 '-azos bis- (cyclohexane carbonitriles) (ABCN, VAZO (registered trademark)), di-t-butyl peroxide, tert-butyl hydrogen
Peroxide, dibenzoyl peroxide and methyl-ethyl-ketone peroxide etc..
And it is possible to use solvent in above-mentioned reaction.Used solvent is not particularly limited at this time, but from reaction
Compound be fluoride in terms of from the point of view of, it is preferable to use fluoride solvent.As fluoride solvent, 1,3- bis trifluoromethyl there are
Benzene, trifluoromethylbenzene, sold by 3M company hydrofluoroether (Hydrofluoroether, HFE) series solvent (NOVEC7100:
C4F9OCH3, NOVEC7200:C4F9OC2H5, NOVEC7300:C2F5-CF(OCH3)-CF(CF3)2Deng) and equally sold by 3M company
Perfluor series solvent (PF5080, PF5070, PF5060 etc.) sold etc..
If it is the manufacturing method of the modified polymer containing fluoro oxyalkylene group of such allyl, complexity is not needed
Manufacturing process can easily manufacture, and can will in addition to water-repellent oil-repellent, release property, chemical resistance, lubricity, durability,
The excellent polymer containing fluoro oxyalkylene group of thermal stability, chemical stability exists other than soil resistance and fingerprint easily wiping property
Industrially advantageously manufacture.
Due to the modified polymer water-repellent oil-repellent containing fluoro oxyalkylene group of allyl of the invention, release property, resistance to
Chemically, lubricity, durability, soil resistance and fingerprint easily wiping property are excellent, therefore the water repellent that can be adapted for paper, fiber etc. is dialled
Oily anti-fouling agent, the lubricant of magnetic recording media, the oil-proofing agent of precision instrument, release agent, cosmetics and protective film etc..Also, with
Previous polymer phase ratio, since thermal stability, chemical stability are excellent, even if to the above-mentioned characteristic of further requirement
Polymer can also be applied.
[embodiment]
Hereinafter, showing embodiment to specifically describe to the present invention, but the present invention is not limited to following embodiments.Separately
Outside, in following examples, number average molecular weight be based on gel permeation chromatography (Gel Permeation Chromatography,
GPC polystyrene scaled value).
[embodiment 1]
It in the reaction vessel, will be by the compound 20g (3.0 × 10 represented by following formula (4-a)-3Mol, quantity average mark
Son amount 3,750) with allyl tributyltin 1.2g (3.6 × 10-3) and hexafluoro meta-xylene (hexafluoro meta- mol
Xylene) 20g is mixed, and is passed through nitrogen.Then, AIBN 0.050g (3.0 × 10 is added-4Mol), with 90 DEG C of stirrings 16
Hour.
Thereafter, reaction product is cooled to room temperature, operates Fen Qu lower layer using liquid separation.Lower layer obtained is utilized into hexane
20g is cleaned, and is cleaned followed by acetone 20g.Solvent under reduced pressure is distillated, is obtained represented by by following formula (1-a)
Single end polymer 17.5g (number average molecular weight containing fluoro oxyalkylene group for having the allyl of allyl modified
3,650).Polymer obtained using hydrogen nuclear magnetic resonance spectroscopy (1H nuclear magnetic resonance
Spectroscopy,1H NMR) confirmation structure.1H NMR: δ 5.65 (1H), δ 4.92 (2H), δ 2.19 (2H), δ 2.01 (2H)
[embodiment 2]
It in the reaction vessel, will be by the compound 20g (1.0 × 10 represented by following formula (4-b)-2Mol, quantity average mark
Son amount 3,850) with allyl tributyltin 4.1g (1.2 × 10-2Mol) and hexafluoro meta-xylene 20g is mixed, and is passed through
Nitrogen.Then, AIBN 0.16g (1.0 × 10 is added-3Mol), stirred 16 hours with 90 DEG C.
Thereafter, reaction product is cooled to room temperature, operates Fen Qu lower layer using liquid separation.Lower layer obtained is utilized into hexane
20g is cleaned, and is cleaned followed by acetone 20g.Solvent under reduced pressure is distillated, is obtained represented by by following formula (1-b)
The two ends polymer 18.4g (number average molecular weight containing fluoro oxyalkylene group that has the allyl of allyl modified
3,650).Polymer obtained utilizes1HNMR confirms structure.1H NMR: δ 5.65 (1H), δ 4.92 (2H), δ 2.19 (2H), δ
2.01(2H)
[embodiment 3]
It in the reaction vessel, will be by the compound 20g (2.5 × 10 represented by following formula (4-c)-3Mol, quantity average mark
Son amount 4,300) with allyl tributyltin 1.2g (3.6 × 10-3Mol) and hexafluoro meta-xylene 20g is mixed, and is passed through
Nitrogen.Then, AIBN 0.050g (3.0 × 10 is added-4Mol), stirred 3 hours with 90 DEG C.
Thereafter, reaction product is cooled to room temperature, operates Fen Qu lower layer using liquid separation.Lower layer obtained is utilized into hexane
20g is cleaned, and is cleaned followed by acetone 20g.Solvent under reduced pressure is distillated, is obtained represented by by following formula (1-c)
Single end polymer 17.0g (number average molecular weight containing fluoro oxyalkylene group for having the allyl of allyl modified
4,200).Polymer obtained utilizes1HNMR confirms structure.1H NMR: δ 5.64 (1H), δ 5.13 (2H), δ 2.80 (2H)
So, it is known that the modified polymer containing fluoro oxyalkylene group of allyl of the invention does not need complicated
Manufacturing process can easily manufacture.
In addition, the present invention is not limited to above embodiment.Above embodiment is to illustrate, and is had and power of the invention
The substantially identical structure of technical idea described in sharp claim, and the technical solution of identical function and effect is played, it is all contained in this
In the technical scope of invention.
Claims (2)
1. a kind of modified polymer containing fluoro oxyalkylene group of allyl, which is characterized in that it is by the following general formula (1) institute
It indicates, and with the number average molecular weight of polystyrene conversion for 1000~50000:
In general formula (1), Rf be the polymer residue m containing fluoro oxyalkylene group of 1 valence perhaps divalent be 1 perhaps 2 X be F or
CF3, the integer that n is 1~10, α is 1 or 2, and when α is 1, aforementioned Rf is by the residue of 1 valence represented by the following general formula (2), α
When being 2, aforementioned Rf is by the residue of the divalent represented by the following general formula (3):
In general formula (2), p is the integer of p > 0 to p=200, and the integer that q is 0~200, r, s are respectively 0, and p+q+r+s=4
~200, each repetitive unit can be arbitrarily bonded, and Y is F or CF3,
In general formula (3), p ' is integer of the p ' > 0 to p '=200, and the integer that q ' is 0~200, r ', s ' they are respectively 0, and p '+
Q '+r '+s '=4~200, each repetitive unit can be arbitrarily bonded, and Y ' is F or CF3。
2. a kind of manufacturing method of the modified polymer containing fluoro oxyalkylene group of allyl, which is characterized in that it is manufacture
The method of the modified polymer containing fluoro oxyalkylene group of allyl described in claim 1, also, it makes by the following general formula
(4) the terminally iodized object polymer containing fluoro oxyalkylene group represented by is deposited with allyl trialkyltin in radical initiator
It reacts under:
In general formula (4), Rf be the polymer residue m containing fluoro oxyalkylene group of 1 valence perhaps divalent be 1 perhaps 2 X be F or
CF3, the integer that n is 1~10, α is 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-242289 | 2013-11-22 | ||
| JP2013242289A JP6130288B2 (en) | 2013-11-22 | 2013-11-22 | Allyl group-modified fluorooxyalkylene group-containing polymer and production method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104650324A CN104650324A (en) | 2015-05-27 |
| CN104650324B true CN104650324B (en) | 2019-06-11 |
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| CN201410677964.XA Active CN104650324B (en) | 2013-11-22 | 2014-11-21 | The modified polymer and its manufacturing method containing fluoro oxyalkylene group of allyl |
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|---|---|
| US (1) | US9228052B2 (en) |
| EP (1) | EP2876127B1 (en) |
| JP (1) | JP6130288B2 (en) |
| CN (1) | CN104650324B (en) |
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| CN110049863B (en) * | 2016-12-13 | 2022-04-01 | 大金工业株式会社 | Stain-proofing article |
| US11820862B2 (en) | 2017-06-30 | 2023-11-21 | Resonac Corporation | Organic fluorine compound, lubricant, and processing method of magnetic recording medium |
| JP7136032B2 (en) * | 2019-07-25 | 2022-09-13 | 信越化学工業株式会社 | Method for producing perfluorooxyalkylene group-containing polymer having reactive silyl group |
| WO2021095878A1 (en) * | 2019-11-13 | 2021-05-20 | ダイキン工業株式会社 | Method for producing fluoropolyether group-containing compound |
| JP2021095474A (en) * | 2019-12-16 | 2021-06-24 | 信越化学工業株式会社 | Perfluoropolyether modified polysilazane and method for producing the same, surface treatment agent, cured coat and article |
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| WO2013121984A1 (en) * | 2012-02-17 | 2013-08-22 | 旭硝子株式会社 | Fluorine-containing ether compound, fluorine-containing ether composition and coating fluid, and substrate having surface-treated layer and method for producing said substrate |
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| BR7105885D0 (en) * | 1970-09-08 | 1973-03-13 | Minnesota Mining & Mfg | PROCESS TO PREPARE ALPHA OMEGADI- (S-TRIAZINYL-DISSUBSTITUTED) -N-PERFLUOR POLIOXA-ALCANOS |
| JPH02188545A (en) * | 1989-01-13 | 1990-07-24 | Nippon Oil & Fats Co Ltd | Polyfluoroalkylpolyoxyalkylene (meth) allyl ether |
| JP3487744B2 (en) * | 1997-10-09 | 2004-01-19 | 信越化学工業株式会社 | Curable composition |
| JP2001192546A (en) * | 2000-01-07 | 2001-07-17 | Shin Etsu Chem Co Ltd | Curable fluoropolyether-based rubber composition |
| JP4412450B2 (en) | 2001-10-05 | 2010-02-10 | 信越化学工業株式会社 | Anti-reflective filter |
| EP1300433B1 (en) | 2001-10-05 | 2008-10-15 | Shin-Etsu Chemical Co., Ltd. | Perfluoropolyether-modified silane, surface treating agent, and antireflection filter |
| JP4012778B2 (en) * | 2002-07-23 | 2007-11-21 | 信越化学工業株式会社 | Perfluoroalkylene ether derivatives having a vinylidene group at one end |
| JP4784743B2 (en) | 2005-02-14 | 2011-10-05 | 信越化学工業株式会社 | Curable perfluoropolyether composition, rubber and gel product using the cured product |
| JP4314493B2 (en) * | 2006-11-02 | 2009-08-19 | 信越化学工業株式会社 | Perfluoropolyether rubber composition for polymer electrolyte membrane and ion conductive polymer electrolyte membrane |
| JP2009117308A (en) * | 2007-11-09 | 2009-05-28 | Shin Etsu Chem Co Ltd | Sealant for dye-sensitized solar cell |
| JP5245902B2 (en) * | 2009-02-20 | 2013-07-24 | 信越化学工業株式会社 | Method for producing fine powdery or pasty polymerization product |
| JP5669257B2 (en) | 2009-10-27 | 2015-02-12 | 信越化学工業株式会社 | Fluorooxyalkylene group-containing polymer composition, surface treatment agent containing the composition, and article surface-treated with the surface treatment agent |
| JP2013023512A (en) * | 2011-07-15 | 2013-02-04 | Nissan Chem Ind Ltd | Heat-resistant coating agent for display containing resin having multiple bond of carbon and carbon |
| KR101743851B1 (en) * | 2012-11-05 | 2017-06-05 | 다이킨 고교 가부시키가이샤 | Silane compound containing perfluoro(poly)ether group |
| JP6020327B2 (en) * | 2013-04-17 | 2016-11-02 | 信越化学工業株式会社 | Photo-curable fluoropolyether gel composition, curing method thereof, gel cured product, and gel product using the cured product |
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2014
- 2014-10-27 US US14/524,313 patent/US9228052B2/en not_active Expired - Fee Related
- 2014-11-04 EP EP14003711.0A patent/EP2876127B1/en active Active
- 2014-11-21 CN CN201410677964.XA patent/CN104650324B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0693087A1 (en) * | 1993-04-06 | 1996-01-24 | AlliedSignal Inc. | Fluorinated photoinitiators and their application in uv curing of fluorinated monomers |
| WO2013121984A1 (en) * | 2012-02-17 | 2013-08-22 | 旭硝子株式会社 | Fluorine-containing ether compound, fluorine-containing ether composition and coating fluid, and substrate having surface-treated layer and method for producing said substrate |
Also Published As
| Publication number | Publication date |
|---|---|
| US9228052B2 (en) | 2016-01-05 |
| CN104650324A (en) | 2015-05-27 |
| US20150148509A1 (en) | 2015-05-28 |
| JP2015101624A (en) | 2015-06-04 |
| EP2876127B1 (en) | 2016-12-21 |
| EP2876127A1 (en) | 2015-05-27 |
| JP6130288B2 (en) | 2017-05-17 |
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